Compositions comprising glyceroglycolipids having an amine linkage as a surfactant or cosurfactant

ABSTRACT

The present invention relates to liquid detergent compositions wherein the detergent active mixture of the compositions comprises 65 to 99% of a glyceroglycolipid compound having an amine linkage and 1 to 35% of a nonionic surfactant. Unexpectedly, applicants have discovered a synergy in the mixture of these surfactants which leads to enhanced detergency.

CROSS REFERENCES

This is a continuation-in-part of Ser. No. 07/816,423 filed Dec. 31,1991.

BACKGROUND OF THE INVENTION

The present invention relates to detergent or personal productcompositions comprising glyceroglycolipids having an amine linkage assurfactants or cosurfactants in the compositions. In particular, theglyceroglycolipid compounds are compounds having 1 to 4 saccharideunits.

Natural glycolipids are known in the art and these structures have beenelucidated. The term glycolipid refers to any of a class of lipids that,upon hydrolysis, yield a sugar (e.g., galactose or glucose), and a lipid(e.g. substituted glycerol group). One major class of these glycolipidsbelong to the glacier glycolipids, i.e., a glycolipids based around aglycerol frame structure. For example, the compound may have a sugarstructure at one end of the glycerol structure instead of an --OH groupand an ester linkage at one or both of the other --H groups that wouldnormally be found on glycerol.

U.S. Pat. No. 3,729,461 to Pomeranz et al., for example, teaches mono-and di-galactosyl glyceride compounds isolated from wheat flour. On oneend of the glycerol frame is found a sugar group (i.e., the mono- ordi-saccharide group) and the two other OH groups normally found on aglycerol are esterified.

In Kobayashi et al., J. Chem Soc. Perkin., Trans. p. 101-103 (1989),there are again taught mono- and di-galactosyl diacylglycerols similarto those taught in Pomeranz et al. Again, there is a sugar group on oneend and a mono- or diester where the remaining two --OH groups on aglycerol would normally be found.

Other ester functionalized mono- and diacyl galactosylglycerols aretaught in Baruah et al., Phytochemistry, 22(8):1741-1744 (1983) and inU.S. Pat. No. 4,859,589 to Godfretsen et al.

Another example of a glyceroglycolipid is a compound having a sugarstructure at one end of a glycerol structure instead of an --OH groupand ether linkage on one or both of the other --OH groups that wouldnormally be found on glycerol.

A glyceroglycolipid containing an ether linkage (where the --OH group onthe glycerol would normally be found) is disclosed in Coulon-Moulec,Bull. Soc. Chem. Biol., 49(7):825-840 (1967); and in Alvarez et al., J.Lipid Res., 31(6):1073-1081 (1990).

These references are concerned, however, only with the synthesis ofvarious lipid glycosides and contains absolutely no teaching orsuggestion that glyceroglycolipids having an ether linkage can be usedas surfactants or cosurfactants in detergent or personal productcompositions.

EP No. 232,851-A (Assigned to National Starch) also appears to teach aglyceroglycolipid with an ether linkage. However, this reference isclearly concerned with compounds used as paper strength additives andneither teaches nor suggests that these compounds may be used assurfactants in detergent or personal wash compositions.

Other examples of glyceroglycolipids having an ether linkage are foundin copending application filed on the same date as the presentapplication.

William et al., Archives of Biochemistry and Biophysics, 195(1):145-151(1979) teach certain alkyl bionamide compounds which are formed bylinking aldobionic acids to an alkylamine through an amide bond. Thecompounds of the invention contain no such amide bond.

Scardera et al. (U.S. Pat. No. 5,023,008) teach a glycerol like framestructure with an amine group on one end. However, this structure has nosugar group on the other end.

Yet another example of a glyceroglycolipid might be a compound with asugar group on one end of the glycerol structure instead of an --OHgroup and an amine group (i.e., NRR¹) at one or both of the other --OHgroups normally found in glycerol, and in particular amines wherein oneor both of R and R¹ are alkyl chains sufficient in length to confersurfactancy properties on the molecule.

U.S. Pat. No. 4,011,169 to Diehl et al., for example, teach enzymecontaining compositions comprising certain aminated polysaccharides asstabilizing agents for enzymes. It is clear from this reference that thepolysaccharides used have at the very least 5 or more saccharide unitsand, preferably, well over 100 (the application notes at column 7, lines50-52, that natural polysaccharides smaller than this are rare).Further, there is a limitation to the amount of elemental nitrogen inthe compound and it seems that compounds with fewer saccharide unitswould not meet this limitation.

U.S. Pat. No. 3,931,148 to Langdon teaches hydroxyalkylamino glycosidecompounds which appear to be similar to those of the invention. However,there appears to be no teaching or suggestion that these compounds canbe used in the specifically claimed detergent and personal productcompositions of the invention.

Finally, because the compounds of the invention are derived fromnaturally occurring carbohydrates, the use of these compounds canprovide a source of renewable raw materials that are syntheticallyversatile and environmentally friendly.

Accordingly, it is an object of this invention to provide novelsurfactants and cosurfactants derived from carbohydrates and the use ofsuch compounds in detergent and personal product compositions.

SUMMARY OF THE INVENTION

The present invention relates to glyceroglycolipid compounds having oneor two amine linkage and to detergent and personal product compositionscomprising these glyceroglycolipids for use as a surfactant orcosurfactant in the compositions. In particular the glyceroglycolipidhas the following formula: ##STR1## wherein A¹ is a saccharide,preferably having one to four saccharide units, more preferably a monoor disaccharide; R or R₁ are the same or different and can be hydrogen,a branched or unbranched, saturated or unsaturated hydrocarbon radical(including aryl, arene, etc.) having 1 to 24, preferably 6 to 18carbons; and B is OH or a NR₂ R₃ group wherein R₂ and R₃ are hydrogen ora branched or unbranched hydrocarbon radical having 1 to 24, preferably6 to 18 carbons. It should be understood that the NRR₁ group and the Bgroup are positionally interchangeable. It should also be understoodthat at least one of R, R₁, R₂ or R₃ must be a hydrocarbon radical(i.e., they may not all be hydrogen at the same time).

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1--Graph of the removal of an oily detergent (triolein) frompolyester using varying ratios of DHAG and C₁₂ EO₃ in a carbonatebuffered solution.

FIG. 2--Graph of the removal of an oily detergent (triolein) frompolyester using varying ratios of DHAG and C₁₂ EO₃ in a borate bufferedsolution.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides detergent and personal productcompositions comprising, as a surfactant or cosurfactant, aglyceroglycolipid compound having the structure set forth below:##STR2## wherein A¹ is a saccharide, preferably having one or moresaccharide units, more preferably a mono- or disaccharide, and mostpreferably a monosaccharide such as glucose or galactose;

R or R₁ are same or different and are hydrogen, a branched or unbranchedhydrocarbon radical (including aryl, arene, etc.) having from about 1 toabout 24, preferably from about 6 to about 18 carbons; and

B is OH or a NR₂ R₃ group, wherein R₂ and R₃ may be the same ordifferent and are hydrogen, a branched or unbranched hydrocarbon radicalhaving 1 to 24, preferably from 6 to 18 carbons; and NRR₁ and B arepositionally interchangeable.

It should also be understood that at least one of R, R₁, R₂ or R₃ mustbe a hydrocarbon radical (i.e., not all may be hydrogen at the sametime) in order to ensure that surfactancy behavior is given to thecompound. Preferably, at least one of these groups should be C₆ -C₂₂,most preferably C₁₀ -C₁₄.

Preferably the compound is a monoalkylamine such that R (or R₁) ishydrogen and R₁ (or R) is an alkyl chain having, for example, 10 to 14carbons.

In a preferred embodiment of the invention, A¹ is a monosaccharide and,in particular, is a galactoside (e.g., D-galactoside), R is a C₁₂ alkylchain, R₁ is hydrogen and B is OH.

Other examples of compounds of the invention (having varying NRR¹ or A¹groups) are set forth below:

3-(butylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(pentylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(hexylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(heptylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(octylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(nonylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(decylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(dodecylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(tetradecylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(hexadecylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(octadecylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(eicosylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(docosylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(tetracosylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(hexenylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(decenylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(dodecenylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(tetradecenylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(hexadecenylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(octadecenylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(docosenylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(tetracosenylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(3-oxa-tridecylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(fluorododecylamino)-2-hydroxypropyl-β-D-Galactopyranoside

3-(butylamino)-2-hydroxypropyl-β-D-Glucopyranoside

3-(pentylamino)-2-hydroxypropyl-β-D-Mannopyranoside

3-(tetradecyloxy)-2-hydroxypropyl-β-D-lactoside

3-(octadecyloxy)-2-hydroxypropyl-β-D-maltoside

3-(octyloxy)-2-hydroxypropyl-β-D-galactotrioside

3-(dodecyloxy)-2-hydroxypropyl-βD-cellotrioside

SYNTHESIS

The glyceroglycolipid of the invention is formed from a precursor havingan epoxide group at the location where the amine linkage is formed andhaving a sugar group. The sugar may be protected or unprotected. Anexample of such a precursor would be the β-D-galactose epoxide compoundhaving the structure: ##STR3##

Once the protected epoxide galactose compound is obtained, this can bereacted with a primary or secondary amine NH₂ R or NHRR₁ (wherein R andR₁ represents the desired chain length of the alkyl groups forming theamine linkage). The amine is added in an inert solvent (e.g.tetrahydrofuran, acetonitrile, dioxane) or neat.

The epoxide precursor used to form the desired surfactant can in turn beformed in a variety of ways.

For example, a galactose epoxide compound may be synthesizedenzymatically via the hydrolysis of lactose in the presence of allylalcohol and β-galactosidase to form a allyl-β-D-galactopyranoside whichcan then be protected and oxidized to the corresponding epoxide withm-chloroperoxybenzoic acid (m-CPBA) in dichloromethane.

This type of reaction, which is taught in Nilsson, K. G. I.,Carbohydrate Research, 180:53-59 (1988) is set forth below: ##STR4##

A chemical mode for preparation of the galactose epoxide involves theuse of acetobromogalactose (2,3,4,6-tetra-O-acetyl-α-D-galactopyranosylbromide) mixed with allyl alcohol and mercuric cyanide. This simpleKoenigs-Knorr glycosydation affords the allyl-β-D-galactopyranosidetetraacetate in very good yield. Oxidation with peracide gives theprotected epoxide sugar. ##STR5##

Once the epoxide precursor is formed, the epoxide is opened with anamine with formation of the amine bond and one free hydroxy group.

COMPOSITIONS

The surfactants of the invention may be used in cleansing or detergentcomposition such as heavy duty liquid detergents (generally enzymecontaining) or powdered detergents. Examples of liquid or powdereddetergents are described in U.S. Pat. No. 4,959,179 to Aronson (forliquid detergent compositions) and U.S. Pat. No. 4,929,379 to Oldenburget al. (for powdered detergent compositions), both of which areincorporated herein by reference.

The liquid detergent compositions of the invention may be built orunbuilt and may be aqueous or nonaqueous. The compositions generallycomprise about 5%-70% by weight of a detergent active material and from0% to 50% of a builder. The composition may comprise 5-70% entirely thesurfactant of the invention or it may comprise a mixture of surfactantswherein the surfactant of the invention comprises 60 to 99% of themixture, preferably 75 to 90% of the mixture.

The liquid detergent compositions of the invention may further comprisean amount of electrolyte (defined as any water-soluble salt) whosequantity depends on whether or not the composition is structured. Bystructured is meant the formation of a lamellar phase sufficient toendow solid suspending capability.

More particularly, while no electrolyte is required for anon-structured, non-suspending composition, at least 1%, more preferablyat least 5% by weight and most preferably at least 15% by weightelectrolyte is used. The formation of a lamellar phase can be detectedby means well known to those skilled in the art.

The water-soluble electrolyte salt may be a detergency builder, such asthe inorganic salt sodium tripolyphosphate or it may be a non-functionalelectrolyte such as sodium sulphate or chloride. Preferably, whateverbuilder is used in the composition comprises all or part of theelectrolyte.

The liquid detergent composition generally further comprises enzymessuch as proteases, lipases, amylases and cellulases which, when present,may be used in amounts from about 0.01 to 5% of the compositions.Stabilizers or stabilizer systems may be used in conjunction withenzymes and generally comprise from about 0.1 to 15% by weight of thecomposition.

The enzyme stabilization system may comprise calcium ion; boric acid,propylene glycol and/or short chain carboxylic acids. The compositionpreferably contains from about 0.01 to about 50, preferably from about0.1 to about 30, more preferably from about 1 to about 20 millimoles ofcalcium ion per liter.

When calcium ion is used, the level of calcium ion should be selected sothat there is always some minimum level available for the enzyme afterallowing for complexation with builders, etc., in the composition. Anywater-soluble calcium salt can be used as the source of calcium ion,including calcium chloride, calcium formate, calcium acetate and calciumpropionate. A small amount of calcium ion, generally from about 0.05 toabout 2.5 millimoles per liter, is often also present in the compositiondue to calcium in the enzyme slurry and formula water.

Another enzyme stabilizer which may be used is propionic acid or apropionic acid salt capable of forming propionic acid. When used, thisstabilizer may be used in an amount from about 0.1% to about 15% byweight of the composition.

Another preferred enzyme stabilizer is polyols containing only carbon,hydrogen and oxygen atoms. They preferably contain from 2 to 6 carbonatoms and from 2 to 6 hydroxy groups. Examples include propylene glycol(especially 1,2 propanediol which is preferred), ethylene glycol,glycerol, sorbitol, mannitol and glucose. The polyol generallyrepresents from about 0.5% to about 15%, preferably from about 1.0% toabout 8% by weight of the composition.

The composition herein may also optionally contain from about 0.25% toabout 5%, most preferably from about 0.5% to abount 3% by weight ofboric acid. The boric acid may be, but is preferably not, formed by acompound capable of forming boric acid in the composition. Boric acid ispreferred, although other compounds such as boric oxide, borax and otheralkali metal borates (e.g. sodium ortho-, meta- and pyroborate andsodium pentaborate) are suitable. Substituted boric acids (e.g.,phenylboronic acid, butane boronic acid and a p-bromo phenylboronicacid) can also be used in place of boric acid.

On especially preferred stabilization system is a polyol in combinationwith boric acid. Preferably, the weight ratio of polyol to boric acidadded is at least 1, more preferably at least about 1.3.

With regard to the detergent active, the detergent active material maybe an alkali metal or alkanolamine soap or a 10 to 24 carbon atom fattyacid, including polymerized fatty acids, or an anionic, a nonionic,cationic, zwitterionic or amphoteric synthetic detergent material, ormixtures of any of these.

Examples of the anionic synthetic detergents are salts (includingsodium, potassium, ammonium and substituted ammonium salts) such asmono-, di- and triethanolamine salts of 9 to 20 carbonalkylbenzenesulphonates, 8 to 22 carbon primary or secondaryalkanesulphonates, 8 to 24 carbon olefinsulphonates sulphonatedpolycarboxylic acids prepared by sulphonation of pyrolyzed product ofalkaline earth metal citrates, e.g., as described in British Patentspecification, 1,082,179, 8 to 22 carbon alkylsulphates, 8 to 24 carbonalkylpolyglycol-ether-sulphates, -carboxylates and -phosphates(containing up to 10 moles of ethylene oxide); further examples aredescribed in "Surface Active Agents and Detergents" (vol. I and II) bySchwartz, Ferry and Bergh. Any suitable anionic may be used and theexamples are not intended to be limiting in any way.

Examples of nonionic synthetic detergents which may be used with theinvention are the condensation products of ethylene oxide, propyleneoxide and/or battalion oxide with 8 to 18 carbon alkylphenols, 8 to 18carbon fatty acid amides; further examples of nonionics include tertiaryamine oxides with 8 to 18 carbon alkyl chain and two 1 to 3 carbon alkylchains. The above reference also describes further examples ofnonionics.

The average number of moles of ethylene oxide and/or propylene oxidepresent in the above nonionics varies from 1-30; mixtures of variousnonionics, including mixtures of nonionics with a lower and a higherdegree of alkoxylation, may also be used.

The nonionic may also be a sugar amide such as a polysaccharide amide.Specifically, the surfactant may be one of the lactobionamides describedin U.S. Ser. No. 816,419 to Au et al., hereby incorporated by reference,or it may be a polyhydroxide amide such as, for example, those describedin U.S. Pat. No. 5,009,814 to Kelkenberg, hereby incorporated byreference in the subject application.

Examples of cationic detergents which may be used are the quaternaryammonium compounds such as alkyldimethylammonium halogenides.

Examples of amphoteric or zwitterionic detergents which may be used withthe invention are N-alkylamine acids, sulphobetaines, condensationproducts of fatty acids with protein hydrolysates; but owing to theirrelatively high costs they are usually used in combination with ananionic or a nonionic detergent. Mixtures of the various types of activedetergents may also be used, and preference is given to mixtures of ananionic and a nonionic detergent active. Soaps (in the form of theirsodium, potassium and substituted ammonium salts) of fatty acids mayalso be used, preferably in conjunction with an anionic and/or nonionicsynthetic detergent.

Builders which can be used according to this invention includeconventional alkaline detergency builders, inorganic or organic, whichcan be used at levels from 0% to about 50% by weight of the composition,preferably from 1% to about 20% by weight, most preferably from 2% toabout 8%.

Examples of suitable inorganic alkaline detergency builders arewater-soluble alkalimetal phosphates, polyphosphates, borates, silicatesand also carbonates. Specific examples of such salts are sodium andpotassium triphosphates, pyrophosphates, orthophosphates,hexametaphosphates, tetraborates, silicates and carbonates.

Examples of suitable organic alkaline detergency builder salts are: (1)water-soluble amino polycarboxylates, e.g., sodium and potassiumethylenediaminetetraacetates, nitrilotriacetates and N-(2hydroxyethyl)-nitrilodiacetates; (2) water-soluble salts of phytic acid,e.g., sodium and potassium phytates (see U.S. Pat. No. 2,379,942); (3)water-soluble polyphosphonates, including specifically, sodium,potassium and lithium salts of ethane-1-hydroxy-1,1-diphosphonic acid;sodium, potassium and lithium salts of methylene diphosphonic acid; andsodium, potassium and lithium salts of ethane-1,1,2-triphosphonic acid.Other examples include the alkali methal salts ofethane-2-carboxy-1,1-diphosphonic acid hydroxymethanediphosphonic acid,carboxylidiphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid,ethane-2-hydroxy-1,1,2-triphosphonic acid,propane-1,1,3,3-tetraphosphonic acid, propane-1,1,2,3-tetraphosphonicacid, and propane-1,2,2,3-tetraphosphonic acid; (4) water soluble saltsof polycarboxylate polymers and copolymers as described in U.S. Pat. No.3,308,067.

In addition, polycarboxylate builders can be used satisfactorily,including water-soluble salts of mellitic acid, citric acid, andcarboxymethyloxysuccinic acid and salts of polymers of itaconic acid andmaleic acid. Other polycarboxylate builders include DPA (dipicolinicacid) and ODS (oxydisuccinic acid). Certain zeolites or aluminosilicatescan be used. One such aluminosilicate which is useful in thecompositions of the invention is an amorphous water-insoluble hydratedcompound of the formula Na_(x) (_(y) AlO.sub. 2.SiO₂), wherein x is anumber from 1.0 to 1.2 and y is 1, said amorphous material being furthercharacterized by a Mg++ exchange capacity of from about 50 mg eq. CaCO₃/g. and a particle diameter of from about 0.01 micron to about 5microns. This ion exchange builder is more fully described in BritishPat. No. 1,470,250.

A second water-insoluble synthetic aluminosilicate ion exchange materialuseful herein is crystalline in nature and has the formula Na_(z)[AlO.sub. 2)_(y).(SiO₂)]xH₂ O, wherein z and y are integers of at least6; the molar ratio of z and y is in the range from 1.0 to about 0.5, andx is an integer from about 15 to about 264; said aluminosilicate ionexchange material having a particle size diameter from about 0.1 micronto about 100 microns; a calcium ion exchange capacity on an anhydrousbasis of at least about 200 milligrams equivalent of CaCO₃ hardness pergram; and a calcium exchange rate on an anhydrous basis of at leastabout 2 grams/gallon/minute/gram. These synthetic aluminosilicates aremore fully described in British Pat. No. 1,429,143.

In addition to the ingredients described hereinbefore, the preferredcompositions herein frequently contain a series of optional ingredientswhich are used for the known functionality in conventional levels. Whilethe detergent compositions are generally premised on aqueous,enzyme-containing detergent compositions, it is frequently desirable touse a phase regulant. This component together with water constitutesthen the solvent matrix for the claimed liquid compositions. Suitablephase regulants are well-known in liquid detergent technology and, forexample, can be represented by hydrotropes such as salts ofalkylarylsulfonates having up to 3 carbon atoms in the alkylgroup, e.g.,sodium, potassium, ammonium and ethanolamine salts of xylene-, toluene-,ethylbenzene-, cumene-, and isopropylbenzene sulfonic acids. Alcoholsmay also be used as phase regulants. This phase regulant is frequentlyused in an amount from about 0.5% to about 20%, the sum of phaseregulant and water is normally in the range from 35% to 65%.

The preferred compositions herein can contain a series of furtheroptional ingredients which are mostly used in additive levels, usuallybelow about 5%. Examples of the like additives include: polyacids, sudsregulants, opacifiers, antioxidants, bactericides, dyes, perfumes,brighteners and the like.

The beneficial utilization of the claimed compositions under varioususage conditions can require the utilization of a suds regulant. Whilegenerally all detergent suds regulants can be utilized, preferred foruse herein are alkylated polysiloxanes such as dimethylpolysiloxane,also frequently termed silicones. The silicones are frequently used in alevel not exceeding 0.5%, most preferably between 0.01% and 0.2%.

It can also be desirable to utilize opacifiers inasmuch as theycontribute to create a uniform appearance of the concentrated liquiddetergent compositions. Examples of suitable opacifiers include:polystyrene commercially known as LYTRON 621 manufactured by MonsantoChemical Corporation. The opacifiers are frequently used in an amountfrom 0.3% to 1.5%.

The compositions herein can also contain known antioxidants for theirknown utility, frequently radical scavengers in the art establishedlevels, i.e., 0.001% to 0.25% (by reference to total composition). Theseantioxidants are frequently introduced in conjunction with fatty acids.

The liquid detergent compositions of the invention may also containdeflocculating polymers such as described in U.S. Ser. No. 664,513,filed Mar. 5, 1991, hereby incorporated by reference.

When the liquid composition is an aqueous composition, the balance ofthe formulation consists of an aqueous medium. When it is in the form ofa non-aqueous composition, the above ingredients make up for the wholeformulation (a non-aqueous composition may contain up to about 5%water).

An ideal liquid detergent composition might contain (all percentages byweight):

(1) 5-70% detergent active system;

(2) 0-50% builder;

(3) 0-40% electrolyte

(4) 0.01-5% enzyme;

(5) 0.1-15% enzyme stabilizer;

(6) 0-20% phase regulant; and

(7) remainder water and minors

The detergent composition of the invention might also be a powdereddetergent composition.

Such powdered compositions generally comprise from about 5-40% of adetergent active system which generally consists of an anionic, anonionic active, a fatty acid soap or mixtures thereof; from 20-70% ofan alkaline buffering agent; up to about 40% builder and balance minorsand water.

The alkaline buffering agent may be any such agent capable of providinga 1% product solution with a DH of above 11.5 or even 12. Advantageousalkaline buffering agents are the alkalimetal silicates, as theydecrease the corrosion of metal parts in washing machines, and inparticular sodium orthometa- or di-silicates, of which sodiummetasilicate is preferred. The alkaline buffering agent is present in anamount of from 0 to 70% by weight, preferably from 0 to 30% by weight.

In addition the compositions of the invention can and normally willcontain detergency builders in an amount of up to 40% by weight andpreferably from 5 to 25% by weight of the total composition.

Suitable builders include sodium, potassium and ammonium or substitutedammonium pyro- and tri-polyphosphates, -ethylene diamine tetraacetates,-nitrilotriacetates, -etherpolycarboxylates, -citrates, -carbonates,-orthophosphates, -carboxymethyloxysuccinates, etc. Other buildersinclude DPA and ODS. Also less soluble builders may be included, such ase.g., an easily dispersible zeolite. Particularly preferred are thepolyphosphate builder salts, nitrilotriacetates, citrates,carboxymethyloxysuccinates and mixtures thereof.

Other conventional materials may be present in minor amounts, providedthey exhibit a good dissolving or dispersing behavior; for examplesequestering agents, such as ethylenediamine tetraphosphonic acid;soil-suspending agents, such as sodiumcarboxymethylcellulose,polyvinylpyrrolidone or the maleic anhydride/vinylmethylether copolymer,hydrotropes; dyes; perfumes; optical brighteners; alkali-stable enzymes;germicides; anti-tarnishing agents; lather depressants; fabric softeningagents; oxygen- or chlorine-liberating bleaches, such asdichlorocyanuric acid salts or alkalimetal hypochlorides.

The remainder of the composition is water.

An ideal powdered detergent composition might contain the following (allpercentages by weight):

(1) 5-40% detergent active system;

(2) 0-40% builder;

(3) 0-30% buffer salt;

(4) 0-30% sulfate;

(5) 0-20% bleach system;

(6) 0-4% enzyme;

(7) minors plus water to 100%.

The surfactants of the invention may also be used in personal productcompositions such as, for example, soap bar compositions, facial or bodycleansing compositions, shampoos for hair or body, conditioners,cosmetic compositions or dental compositions.

In one embodiment of the invention, the surfactant of the invention maybe used, for example, in a toilet bar (i.e. soap and/or detergent bar)formulation.

Typical toilet bar compositions are those comprising fatty acid soapsused in combination with a detergent other than fatty acid soap and freefatty acids. It should be noted that the composition may comprise nofatty acid soap and may be based on actives other than fatty acid soap.Mildness improving salts, such as alkali metal salt or isethionate, arealso typically added. In addition other ingredients, such as germicides,perfumes, colorants, pigments, suds-boosting salts and anti-mushingagents may also be added.

Fatty acid soaps are typically alkali metal or alkanol ammonium salts ofaliphatic alkane or alkene monocarboxylic acids. Sodium, potassium,mono-, di- and tri-ethanol ammonium cations, or combinations thereof,are suitable for purposes of the invention. The soaps are well knownalkali metal salts of natural or synthetic aliphatic (alkanoic oralkenoic) acids having about 8 to 22 carbons, preferably 12 to about 18carbons.

Examples of soap which may be used may be found in U.S. Pat. No.4,695,395 to Caswell et al. and U.S. Pat. No. 4,260,507 (Barrett), bothof which are incorporated herein by reference.

In a soap-based bar, fatty acid soaps will generally comprise greaterthan 25% of the composition, generally from 30-95%. Preferably, theamount of soap will range from 40% to 70% by weight of the composition.

In a bar based on other actives, soap may comprise 0-50% by weight. Ingeneral C₈ to C₂₄ fatty acid comprises 5-60% of the composition.

The compositions will also generally comprise a non-soap detergent whichis generally chosen from anionic, nonionic, cationic, zwitterionic oramphoteric synthetic detergent materials or mixtures thereof. Thesesurfactants are all well known in the art and are described, forexample, in U.S. Pat. Nos. 4,695,395 and 4,260,507 discussed above. Onepreferred non-soap anionic is a C₈ -C₂₂ akyl isethionate. These estermay be prepared by the reaction between alkali metal isethionate andmixed aliphatic fatty acids having from 8 to 22 carbons. The non-soapactives may comprise from 0 to 50% of the composition.

A certain amount of free fatty acids of 8 to 22 carbons are alsodesirably incorporated into soap compositions to act as superfattingagents or as skin feel and creaminess enhancers. If present, the freefatty acids comprise between 1 and 15% of the compositions.

A preferred mildness improving salt which may be added to soapcompositions is a simple unsubstituted sodium isethionate. This may bepresent as 0.1 to 50% of the composition, preferably 0.5% to 25%, morepreferably 2% to about 15% by weight. Other mildness co-actives whichmay be used include betain compounds or ether sulphates. These also maybe present at 0.1 to 50% of the composition, preferably 0.5% to 25%.

The sulfate ester surfactant may comprise 0.01 to 45% by weight of thecomposition (as the monoester), preferably 25% to 40%, and 0.01% to 10%of the composition (as the diester), preferably 0.01% to 5%.

Other optional ingredients which may be present in soap bar compositionsare moisturizers such as glycerin, propylene glycol, sorbitol,polyethylene glycol, ethoxylated or methoxylated ether of methyl glucoseetc; water-soluble polymers such as collagens, modified cellulases (suchas Polymer JR(®)), guar gums and polyacrylates; sequestering agents suchas citrate, and emollients such as silicones or mineral oil. Anotheruseful set of ingredients are various cosurfactants and non-soapdetergents.

In a second embodiment of the invention, the glycerol frame surfactantwith ether linkage of the invention may be present in a facial or bodycleansing composition. Examples of such cleaning compositions aredescribed, for example, in U.S. Pat. No. 4,812,253 to Small et al. andU.S. Pat. No. 4,526,710 to Fujisawa, both of which are herebyincorporated by reference.

Typically, cleansing compositions will comprise a fatty acid soaptogether with a non-soap surfactant, preferably a mild syntheticsurfactant. Cleaning compositions will also generally include amoisturizer or emollient and polymeric skin feel and mildness aids. Thecompositions may further optionally include thickener (e.g. magnesiumaluminum silicate, carbopol), conditioners, water soluble polymers (e.g.carboxymethyl cellulose), dyes, hydrotropes brighteners, perfumes andgermicides.

The fatty acid soaps used are such as those described above in uses indetergent bar formulations. These soaps are typically alkali metal oralkanol ammonium salts of aliphatic or alkene monocarboxylic salts.Sodium, potassium, mono-, di- and triethanol ammonium cations, orcombinations thereof are suitable. Preferred soaps are 8 to 24 carbonhalf acid salts of, for example, triethanolamine.

Surfactants can be chosen from anionic, nonionic, cationic, zwitterionicor amphoteric materials or mixtures thereof such as are described inU.S. Pat. No. 4,695,395 mentioned above, or in U.S. Pat. No. 4,854,333to Inman et al, hereby incorporated by reference.

Moisturizers are included to provide skin conditioning benefits andimprove mildness. This term is often used as synonymous with emollientand is then used to describe a material which imparts a smooth and softfeeling to skin surface.

There are two ways of reducing water loss from the stratum corneum. Oneis to deposit on the surface of the skin an occlusive layer whichreduces the rate of evaporation. The second method is to addnonocclusive hydgroscopic substances to the stratum corneum which willretain water, and make this water available to the stratum corneum toalter its physical properties and produce a cosmetically desirableeffect. Nonocclusive moisturizers also function by improving thelubricity of the skin.

Both occlusive and nonocclusive moisturizers can work in the presentinvention. Some examples of moisturizers are long chain fatty acids,liquid water-soluble polyols, glycerin, propylene glycol, sorbitol,polyethylene glycol, ethoxylated/propoxylated ethers of methyl glucose(eg., methyl gluceth-20) and ethoxylated/-propoxylated ethers of lanolinalcohol (e.g., Solulan-75).

Preferred moisturizers are coco and tallow fatty acids. Some otherpreferred moisturizers are the nonoclusive liquid water soluble polyolsand the essential amino acid compounds found naturally in the skin.

Other preferred nonocclusive moisturizers are compounds found to benaturally occurring in the stratum corneum of the skin, such as sodiumpyrrolidone carboxylic acid, lactic acid, urea, L-proline, guanidine andpyrrolidone. Examples of other nonocclusive moisturizers includehexadecyl, myristyl, isodecyl or isopropyl esters of adipic, lactic,oleic, stearic, isostearic, myristic or linoleic acids, as well as manyof their corresponding alcohol esters (sodium isostearoyl-2 lactylate,sodium capryl lactylate), hydrolyzed protein and other collagen-derivedproteins, aloe vera gel and acetamide MEA.

Some occlusive moisturizers include petrolatum, mineral oil, beeswax,silicones, lanolin and oil-soluble lanolin derivatives, saturated andunsaturated fatty alcohols such as behenyl alcohol, squalene andsqualane, and various animal and vegetable oils such as almond oil,peanut oil, wheat germ oil, linseed oil, jojoba oil, oil of apricotpits, walnuts, palm nuts, pistachio nuts, sesame seeds, rapeseed, cadeoil, corn oil, peach pit oil, poppyseed oil, pine oil, castor oil,soybean oil, avocado oil, safflower oil, coconut oil, hazelnut oil,olive oil, grape seed oil and sunflower seed oil.

Other examples of both types of moisturizers are disclosed in"Emollients--a Critical Evaluation," by J. Mausner, Cosmetics &Toiletries, May, 1981, incorporated herein by reference.

The polymeric skin feel and mildness aids useful in the presentinvention are the cationic, anionic, amphoteric, and the nonionicpolymers used in the cosmetic field. Reduced skin irritation benefits asmeasured by patch testing of cationic and nonionic types of polymers areset out in "Polymer JR for Skin Care" Bulletin, by Union Carbide, 1977.The cationics are preferred over the others because they provide betterskin feel benefits.

The amount of polymeric skin feel and mildness aids found useful in thecomposition of the present invention is from about 0.01% to about 5%,preferably from about 0.3% to about 4%. In bar compositions with lessthan 5.5% soap, the polymer is used at a level of 2% to 5%, preferably3% or more.

Other types of high molecular weight polymeric skin feel and skinmildness aids, such as nonionic guar gums, Merquats 100 and 550, made byMerck & Co, Inc.; Jaguar C-14-S made by Stein Hall; Mirapol a15 made byMiranol Chemical Company, Inc.; and Galactasol 811, made by Henkel,Inc.; plus others, are usable. The polymer also provides enhanced creamylather benefits.

The nonionic polymers found to be useful include the nonionicpolysaccharides, e.g., nonionic hydroxypropyl guar gums, offered byCelanese Corp. A preferred nonionic hydroxypropyl guar gum material isJaguar® R HP-60 having molar substitution of about 0.6. Another class ofuseful nonionics is the cellulosic nonionic polymers, e.g., HEC and CMC.

The cationic polymers employed in this invention also provide adesirable silky, soft, smooth in-use feeling. The preferred level forthis invention is 0.1-5% of the composition. There is reason to believethat the positively charged cationic polymers can bind with negativelycharges sites on the skin to provide a soft skin feel after use. Not tobe bound by any theory, it is believed that the greater the chargedensity of the cationic polymer, the more effective it is for skin feelbenefits.

Other suitable cationic polymers are copolymers ofdimethylaminoethylmethacrylate and acrylamide and copolymers ofdimethyldiallylammonium chloride and acrylamide in which the ratio ofthe cationic to neutral monomer units has been selected to give acopolymer having a cationic charge. Yet other suitable types of cationicpolymers are the cationic starches, e.g., Sta-Lok®300 and 400 made byStaley, Inc.

A more complete list of cationic polymers useful in the presentinvention is described in U.S. Pat. No. 4,438,095, to Grollier/allec,issued Mar. 20, 1984, incorporated herein by reference. Some of the morepreferred cationics are listed in Col. 3, Section 2; Col. 5, section 8;Col. 8, section 10; and Col. 9, lines 10-15 of the Grollier/allecpatent, incorporated herein by reference.

In a third embodiment of the invention, the surfactant of the inventionmay be used, for example, in a shampoo. Examples of such compositionsare described in U.S. Pat. No. 4,854,333, to Inman and U.S. Pat. No.4,526,710 to Fujisawa, both of which are hereby incorporated byreference.

The shampoo compositions which may be used typically comprise asurfactant selected from any one of a wide variety of surfactants knownin the art (such as those described in U.S. Pat. No. 4,854,333,incorporated herein by reference). The shampoo compositions mayadditionally comprise a compound considered useful for treatingdandruff, e.g. selenium sulfide.

The compositions all may also optionally comprise a suspending agent,for example, any of several acyl derivative materials or mixturesthereof. Among these are ethylene glycol esters of fatty acids having 16to 22 carbons. Preferred suspending agents include ethylene glycolstearates, both mono- and distearate. Preferred alkanol amides arestearic monoethanolamide, stearic diethanolamide and stearicmonoisopropanolamide. Still other long chain acyl derivatives includelong chain esters of long chain fatty acids (e.g., stearyl stearate,cetyl palmitate), glyceryl esters (e.g. glyceryl distearate), and longchain esters of long chain alkanol amides (e.g., stearamide DEAdistearate, stearamide MEA stearate).

Still other suitable suspending agents are alkyl (16 to 22 carbon)dimethyl amine oxides, such as stearyl dimethyl amine oxide. If thecompositions contain an amine oxide or a long chain acyl derivative as asurfactant, these components may also provide the suspending functionand additional suspending agent may not be needed.

Xanthan gum is another agent used to suspend, for example, seleniumsulfide which may be in the present compositions. This biosynthetic gummaterial is commercially available and is a heteropolysaccharide with amolecular weight of greater than 1 million. It is believed to containD-glucose, D-mannose and D-glucuronate in the molar ratio of2.8:2.0:2.0. The polysaccharide is partially acetylated with 4.7%acetyl. Supplemental information on these agents is found in Whistler,Roy L. (Editor), Industrial Gums--Polysaccharides and Their DerivativesNew York: Academic Press, 1973. Kelco, a Division of Merck & Co., Inc.,offers xanthan gum as Keltrol®.

A particularly preferred suspending system comprises a mixture ofxanthan gum, present at a level of from about 0.05% to about 1.0%,preferably from about 0.2% to about 0.4%, of the compositions, togetherwith magnesium aluminum silicate (Al₂ Mg₈ Si₂), present at a level offrom about 0.1% to about 3.0%, preferably from about 0.5% to about 2.0%,of the compositions. Magnesium aluminum silicate occurs naturally insuch smectite minerals as colerainite, saponite and sapphire. Refinedmagnesium aluminum silicates useful herein are readily available, forexample as veegum, manufactured by R.T. Vanderbilt Company, Inc.Mixtures of suspending agents are also suitable for use in thecompositions of this invention.

Other useful thickening agents are the cross-linked polyacrylates suchas those manufactured by B. F. Goodrich and sold under the Carbopol(®)tradename.

Another optional component for use in the present compositions is anamide. The amide used in the present compositions can be any of thealkanolamides of fatty acids known for use in shampoos. These aregenerally mono- and diethanolamides of fatty acids having from about 8to 24 carbon atoms. Preferred are coconut monoethanolamide, lauricdiethanolamide and mixtures thereof. The amide is present at a level offrom about 1% to about 10% of the compositions.

The compositions may also contain nonionic polymer material which isused at a low level to aid in dispersing particles. The material can beany of a large variety of types including cellulosic materials such ashydroxypropyl methyl cellulose, carboxymethyl cellulose, hydroxyethylcellulose and sodium carboxymethyl cellulose as well as mixtures ofthese materials.

Other materials include alginates, polyacrylic acids, polyethyleneglycol and starches, among many others. The nonionic polymers arediscussed in detail in Industrial Gums, edited by Roy L. Whistler,academic Press, Inc., 1973, and Handbook of Water-Soluble Gums andResins, edited by Robert L. Davidson, McGraw-Hill, Inc., 1980. Both ofthese books in their entirety are incorporated herein by reference.

When included, the nonionic polymer is used at a level of from about0.001% to about 0.1%, preferably from about 0.002% to about 0.05%, ofthe composition. Hydroxypropyl methyl cellulose is the preferredpolymer.

Another suitable optional component useful in the present compositionsis a nonvolatile silicone fluid.

The nonvolatile silicone fluid may be either a polyalkyl siloxane, apolyaryl siloxane, a polyalkylarly siloxane or a polyether siloxanecopolymer and is present at a level of from about 0.1% to about 10.0%,preferably from about 0.5% to about 5.0%. Mixtures of these fluids mayalso be used and are preferred in certain executions. The dispersedsilicone particles should also be insoluble in the shampoo metrix. Thisis the meaning of "insoluble" as used herein.

The essentially nonvolatile polyalkyl siloxane fluids that may be usedinclude, for example, polydimethyl siloxanes with viscosities rangingfrom about 5 to about 600,000 centistokes at 25° C. These siloxanes areavailable, for example, from the General Electric Company as theViscasil series and from Dow Corning as the Dow Corning 200 series. Thesiloxane viscosity can be measured by means of a glass capillaryviscometer as set forth in Dow Corning Corporate Test Method CTM0004,Jul. 20, 1970. Preferably the viscosity of the these siloxanes rangefrom about 350 centistokes to about 100,000 centistokes.

The essentially nonvolatile polyether siloxane copolymer that may beused is, for example, a polypropylene oxide modifieddimethylpolysiloxane (e.g., Dow Corning DC-1248), although ethyleneoxide or mixtures of ethylene oxide and propylene oxide may also beused.

Suitable silicone fluids are described in U.S. Pat. No. 2,826,551, Geen;U.S. Pat. No. 3,946,500, Jun. 22, 1976, Drakoff; U.S. Pat. No.4,364,837, Pader; and British Patent 849,433, Woolston. All of thesepatents are incorporated herein by reference. Also incorporated hereinby reference is Silicon Compounds, distributed by Petrarch Systems,Inc., 1984. This reference provides a very good listing of suitablesilicone materials.

Another silicone material useful is silicone gum. Silicone gums aredescribed by Petrarch and others including U.S. Pat. No. 4,152,416, May1, 1979, Spitzer, et al., and Noll, Chemistry and Technology ofSilicones, New York, academic Press, 1968. Useful silicone gums are alsodescribed in General Electric Silicone Rubber Product Data Sheets SE 30,SE 33, SE 54 and SE 76. all of these references are incorporated hereinby reference. "Silicone gum" materials denote high molecular weightpolydiorganosiloxanes having a mass molecular weight of from about200,000 to about 1,000,000. Specific examples includepolydimethylsiloxane, (polydimethylsiloxane) (methylvinylsiloxane)copolymer, poly(dimethylsiloxane) (diphenyl) (methylvinylsiloxane)copolymer, and mixtures thereof. Mixtures of silicone fluids andsilicone gums are also useful herein.

The shampoos herein can contain a variety of other nonessential optionalcomponents suitable for rendering such compositions more formulatable,or aesthetically and/or cosmetically acceptable. Such conventionaloptional ingredients are well-known to those skilled in the art andinclude, e.g., preservatives, such as benzyl alcohol, methyl paraben,propyl paraben, and imidazolinidyl urea; cationic surfactants, such ascetyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride,tricetyl methyl ammonium chloride, stearyldimethyl benzyl ammoniumchloride, and di(partially hydrogenated tallow) dimethylammoniumchloride; menthol; thickeners and viscosity modifiers, such as blockpolymers of ethylene oxide and propylene oxide such as Pluronic F88offered by BaSa Wyandotte, sodium chloride, sodium sulfate, propyleneglycol, and ethyl alcohol; pH adjusting agents, such as citric acid,succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate;perfumes; dyes; and sequestering agents, such as disodiumethylenediamine tetraacetate. Such agents generally are usedindividually at a level of from about 0.01% to about 10%, preferablyfrom about 0.5% to about 5.0%, of the composition.

A typical shampoo composition may comprise (percentages by weight ):

(1) 5-15% active of invention;

(2) 0-10% anionic coactive;

(3) 0-10% amphoteric coactive;

(4) 0-5% lauramide MEA;

(5) 0-5% thickener;

(6) 0-2% fragrance;

(7) 0-1% preservative; and

(8) remainder water.

In a fourth embodiment of the invention, the surfactant of the inventionmay be used in a conditioner composition such as is taught and describedin U.S. Pat. No. 4,913,828 to Caswell et al. which is herebyincorporated by reference.

More particularly, conditioner compositions are those containing aconditioning agent (e.g. alkylamine compounds) such as those describedin U.S. Pat. No. 4,913,828.

A typical condition composition may comprise (percentages by weight):

(a) 1-98% surfactant of invention, preferably 10 to 60% (or 1-98% or 10to 60% surfactant mixture comprising the surfactant of invention andwherein cosurfactant(s) are selected from the group consisting ofanionics, nonionics, ampholytics, zwitterionics and cationionics);

(b) 0-80% builder (e.g. , polycarboxylates);

(c) 0-10% chelating agent (e.g., amino carboxylates);

(d) 0-5% soil release agents (e.g., derivatives of hydroxyethercellulosic polymers);

(e) 0-5% anti redeposition agent (e.g., protease)

(f) 0-2% enzyme (e.g. , protease);

(g) 0.01-20% conditioning agent (e.g., cationic surfactant);

(h) 0.1-10% stabilizer for conditioner (e.g., clays or polysaccharideagents);

(i) water and minors to 100%

If formulated as conditioner shampoo, the composition may comprise:

(a) 5-60% surfactant (wholly the surfactant of invention or comprisingthe surfactant of invention);

(b) 1-60% conditioner (e.g., cationic);

(c) 0-2% preservative (e.g., benzyl alcohol);

(d) 0-10% thickener (e.g., diethanalomide); and

(e) remainder water and minors.

In a fifth embodiment of the invention, the surfactant may be used in acosmetic composition, such as is taught and is described in EP0,371,803.

Such compositions generally comprise thickening agents, preservativesand further additions.

The composition may comprise polymer thickener in an amount sufficientto adjust the viscosity of the composition, so as to facilitatedispensing it conveniently onto the body surface.

Examples of polymer thickeners include: anionic cellulose materials,such as sodium carboxy methyl cellulose; anionic polymers such ascarboxy vinyl polymers, for example, Carbomer 940 and 941; nonioniccellulose materials, such as methyl cellulose and hydroxy propyl methylcellulose; cationic cellulose materials, such as Polymer JR 400;cationic gum materials, such as Jaguar C13 S; other gum materials suchas gum acacia, gum tragacanth, locust bean gum, guar gum andcarrageenan; proteins, such as albumin and protein hydrolysates; andclay materials, such as bentonite, hectorite, magnesium aluminumsilicate, or sodium magnesium silicate.

Generally, the thickening agent may comprise from 0.05 to 5%, preferably0.1 to 1% by weight of the composition.

The composition according to the invention can also optionally comprisea preservative to prevent microbial spoilage.

Examples of preservatives include:

(i) Chemical preservatives, such as ethanol, benzoic acid, sodiumbenzoate, sorbic acid, potassium sorbate, sodium propionate and themethyl, ethyl, propyl and butyl esters of p-hydroxybenzoic acid2-bromo-2-nitropropane-1, 3-diol, phenoxyethanol, dibromodicyanobutane,formalin and Tricolsan. The amount of chemical preservative optionallyto be incorporated in the composition according to the invention willgenerally be from 0.05 to 5%, preferably from 0.01 to 2% by weight, theamount chosen being sufficient to arrest microbial proliferation.

(ii) Water activity depressants, such as glycerol, propylene glycol,sorbitol, sugars and salts, for examples alkali metal halides, sulphatesand carboxylates. When employing a water activity depressant, sufficientshould be incorporated in the composition according to the invention toreduce the water activity from 1 to <0.9, preferably to <0.85 and mostpreferably 0.8, the lowest of these values being that at which yeasts,molds and fungi will not proliferate.

The composition can also contain other optional adjuncts, which areconventionally employed in compositions for topical application to humanskin. These adjuncts, when present, will normally form the balance ofthe composition.

Examples of optional adjuncts include vehicles, the selection of whichwill depend on the required product form of the composition. Typically,the vehicle when present, will be chosen from diluents, dispersants orcarriers for the dialkyl or dialkenyl phosphate salt so as to ensure aneven distribution of it when applied to the skin.

Compositions according to this invention can include water as a vehicle,usually with at least one other cosmetically-acceptable vehicle.

Vehicles other than water that can be used in compositions according tothe invention can include liquids or solids as emollients, solvents,humectants, thickeners and powders. Examples of each of these types ofvehicles, which can be used singly or as mixtures of one or morevehicles, are as follows:

Emollients, such as stearyl alcohol, glyceryl monolaurate, glycerylmonoricinoleate, glyceryl monostearate, propane-1, 2-diol, butane-1.3diol, docosan-1,2-diol, mink oil, cetyl alcohol, isopropyl isostearate,stearic acid, isobutyl palmitate, isocetyl stearate, oleyl alcohol,isopropyl laurate, hexyl laurate, decyl oleate, octadecan-2-ol, isocetylalcohol, eicosanyl alcohol, behenyl alcohol, cetyl palmitate, siliconeoils such as dimethylpolysiloxane, di-n-butyl sebacate, isopropylmyristate, isopropyl palmitate, isopropyl stearate, butyl stearate,polyethylene glycol, triethylene glycol, lanolin, cocoa butter, cornoil, cotton seed oil, tallow, lard, olive oil, palm kernel oil, rapeseedoil, safflower seed oil, soybean oil, sunflower seed oil, olive oil,sesame seed oil, coconut oil, arachis oil, castor oil, acetylatedlanolin alcohols, petroleum, mineral oil, butyl myristate, isostearicacid, palmitic acid, isopropyl linoleate, lauryl lactate, myristyllactate, decyl oleate, myristyl myristate;

Propellants, such as trichlorofluoromethane, dichlorodifluoromethane,dichlorotetrafluoromethane, monochlorodifluoromethane,trichlorotrifluoromethane, propane, butane, isobutane, dimethyl ether,carbon dioxide, nitrous oxide;

Solvents, such as ethyl alcohol, methylene chloride, isopropanol,acetone, castor oil, ethylene glycol monoethyl ether, diethylene glycolmonobutyl ether, diethylene glycol monoethyl ether, dimethyl sulphoxide,dimethyl formamide, tetrahydrofuran;

Humectants, such as glycerin, sorbitol, sodium2-pyrrolidone-5-carboxylate, soluble collagen, dibutyl phthalate,gelatin;

Powders, such as chalk, talc, fullers earth, kaolin, starch, gums,colloidal silicon dioxide, sodium polyacrylate, tetra alkyl and/ortrialkyl aryl ammonium smectites, chemically modified magnesium aluminumsilicate, organically modified montmorillonite clay, hydrated aluminumsilicate, fumed silica, carboxyvinyl polymer, sodium carboxymethylcellulose, ethylene glycol monostearate.

The cosmetically acceptable vehicle, when present, will usually formfrom 0.01 to 99.9%, preferably from 59 to 98% by weight of thecomposition, and can, in the absence of other cosmetic adjuncts, formthe balance of the composition.

A wide variety of conventional sunscreening agents, such as thosedescribed in U.S. Pat. No. 4,919,934 to Deckner et al. herebyincorporated by reference, may also be used in the cosmetic compositionsof the invention.

Such agents include, for example, p-aminobenzoic acid, its salts and itsderivatives, anthranilates, salicylates, cinnamic acid derivatives, di-and trihydroxy cinnamic acid derivatives, hydrocarbons such asdiphenylbutadiene and stilbene, dibenzalacetone and benzalacetophenone,naphthasulfonates, di-hydroxy naphthloic acid and its salts, hydroxydiphenylsulfonates, coumarin derivatives, diazoles, quinine salts,quinoline derivatives, hydroxy or methoxy substituted benzophenones,uric or vilouric acid, tannic acid and its derivatives, hydroquinone,and benzophenones.

In a sixth embodiment of the invention, the surfactant may be used in atoothpaste composition such as is taught and is described in U.S. Pat.No. 4,935,227 to Duckworth, which is hereby incorporated by reference.

Such compositions generally comprise abrasive gels (e.g. calciumcarbonate), oral therapeutic agents (e.g., flourine containingcompound), coactives, flavoring agents, sweetening agents, humectantsand binding or thickening gels.

Preferred toothpastes of this invention comprise 0 to 1.5% by weight ofanionic surfactant. In more preferred products the amount of anionicsurfactant is 0 to 1% by weight with most preferred amounts being 0 to0.75% by weight.

Toothpastes of this invention may include other surfactants, especiallynon-ionic surfactants.

Toothpaste of the invention will also comprise the usual additionalingredients in particular humectant binder or thickening agent.

Humectants which may be used include glycerol, sorbitol syrup,polyethylene glycol, lactitol, xylitol or hydrogenated corn syrup. Thetotal amount of humectant present will generally range from 10% to 85%by weight of the toothpaste.

Numerous binding or thickening agents have been indicated for use intoothpastes, preferred ones being sodium carboxymethylcellulose,cross-linked polyacrylates and xanthan gum. Others include natural gumbinders such as gum tragacanth, gum karaya and gum arabic, Irish moss,alginates, and carrageenans. Silica thickening agents include the silicaaerogels and various precipitated silicas. Mixtures of binders andthickeners may be used. The amount of binder and thickening agentincluded in a toothpaste is generally between 0.1 and 15% by weight.

In a seventh embodiment of the invention, the molecule of the inventionmay be used in a light duty liquid detergent composition such as thosetaught in U.S. Pat. No. 4,671,894 to Lamb et al., U.S. Pat. No.4,368,146 to Aronson et al., and U.S. Pat. No. 4,555,360 to Bissett etal., all of which are hereby incorporated by reference, into the subjectapplication.

Generally such compositions comprise a mixture of sulphate andsulphonate anionic surfactants together with a suds stabilizing agent.These compositions may also comprise nonionic surfactants designed toreduce the level of non-performing ingredients such as solvents andhydrotropes and zwitterionic surfactants for providing enhanced greaseand particulate soil removal performance. Among other ingredients whichmay also be used in such compositions are opacifiers (e.g. ethyleneglycol distearate), thickeners (e.g., guar gum), antibacterial agents,antitarnish agents, heavy metal chelators (e.g. ETDA), perfumes anddyes.

A typical light duty liquid composition may comprise (all percentages byweight):

(a) 0.01-65% anionic surfactant;

(b) 0.01-50% surfactant of invention;

(c) 0-8% suds promoting agent (e.g., alkyl alcohol amide);

(d) 0-10% hydrotrope (e.g., benzene sulfonate); and

(e) minors plus water to 100%.

In an eighth embodiment of the invention the molecule of the inventionmay be used in underarm deodorant/antiperspirant compositions such asthose taught in U.S. Pat. No. 4,919,934 to Deckner, U.S. Pat. No.4,944,937 to McCall and U.S. Pat. No. 4,944,938 to Patini, all of whichpatents are hereby incorporated by reference.

Such compositions generally comprise a cosmetic stick (gel or wax)composition which in turn generally comprises one or more liquid basematerials (e.g., water, fatty acid and fatty alcohol esters,water-insoluble ethers and alcohols, polyorganosiloxanes); a solidifyingagent for solidifying the liquid base; and an active component such asbacteriostats or fungistats (for anti-deodorant activity) or astringentmetallic salts (for antiperspirant activity).

These compositions may also comprise hardeners, strengtheners,emollients, colorants, perfumes, emulsifiers and fillers.

While various compositions are described above, these should not beunderstood to be limiting as to what other personal product compositionsmay be used since other compositions which may be known to those ofordinary skill in the art are also contemplated by this invention.

The invention is set forth in greater detail in the example which followbelow. These examples are merely to illustrate the invention and are notintended to be limiting in any way.

EXAMPLE 1 Synthesis of3-(N,N-dibutylamino)-2-hydroxypropyl-β-D-galactopyranoside

Acetobromogalactose (2,3,4,6-tetra-O-acetyl-α-D-galactopyranosylbromide) was mixed with allyl alcohol and mercuric cyanide via theKoenigs-Knorr glycosylation to obtain allyl-β-D-galactopyranosidetetraacetate. This was followed by oxidation with 3-chloroperoxybenzoicacid in dichloromethane to obtain 2,3-epoxypropyl-β-D-galactopyranoside,2,3,4,6-0-tetracetate.

In a 35 ml two neck flask was added 0.32 g (0.8 mmoles) of the aboveidentified epoxide compound and 1.5 ml of dry acetonitrile, followed bydropwise addition of N,N-dibutylamine (0.2 g, 1.6 mmoles). The reactionwas allowed to run at room temperature and was followed by thin layerchromotography using a 9:1 CHCl₃ :MeOH with a drop of ammonium hydroxideas eluent. Rf value of the new product was found to be 0.36 (the Rf ofstarting epoxide prior to consumption had been 0.80).

Column chromatography was used to separate the ring-opened adduct fromthe excess amine using a 9:1CHCl₃ :MeOH with a drop of ammoniumhydroxide as eluent. Total yield of this syrupy ring-opened product was0.40 g. The product was confirmed by NMR and M.S.

The product was further deprotected using catalytic amounts of sodiummethoxide in 20 ml of anhydrous methanol. TLC (Thin layerchromatography) showed that after 8 hours the product was completelydeacetylated. The deacetylated product was passed through a shortsilica-gel column (8:2 CHCl₂ :methanol) to yield 0.175 g of the finalproduct, 3-(N,N-dibutylamino)-2-hydroxypropyl-β-D-galactopyranoside.

EXAMPLE 2

In a 50 ml, 2 neck flask is added 1 gram of 2,3-epoxypropyl β-Dgalactopyranoside 2,3,4,6-0-tetraacetate (epoxide compound). 10 ml ofanhydrous acetonitrile, and 2-10 equivalents of a primary or secondaryamine. Reaction is allowed to stir at 20°-80° C. and is followed by thinlayer chromatography using a 9:1 CHCl₃ :MeOH with a drop of ammoniumhydroxide as eluent. More amine can be added to ensure all the epoxideis reacted. The ring-opened product is isolated and the acetate groupsare removed if necessary, with catalytic amounts of sodium methoxide inanhydrous methanol. The product is further purified by passing through asilica gel column.

With regard to Examples 1 and 2 above, while it would not necessarily beexpected for the3-(N,N-dibutylamino)-2-hydroxypropyl-β-D-galactopyranoside of Example 1to have optimal surfactancy (because of butyl groups), longer chaingroups (e.g., C₆ -C₂₀, preferably C₈ -C₁₄) can be prepared in the samemanner or as described in Example 2 (where the primary or secondaryamine added to epoxide would have, for example, C₁₀ -C₁₄ groups).Preferably, in Example 2, a n-monoalkylamine (e.g., NH₂ C₁₂ H₂₅) wouldbe used.

EXAMPLE 3 Surface Activity and Detergency

Detergency performance was assessed in triolein removal experimentsusing Terg-O-Tometer. ³ H radio-labelled triolein was used to assesssoil removal; subsequent to the wash, 4×1 ml samples of wash liquor wasremoved from each pot and the activity determined using a liquidscintillation counter. Percentage detergency was calculated from therelationship: ##EQU1## where A_(w) is the total activity in the washliquor and A_(s) is the level of activity originally applied to thecloth.

Wash conditions are given below:

    ______________________________________                                        Apparatus        Terg-O-Tometer UR 7227                                       Wash Time        20 minutes                                                   Agitation        70 rpm                                                       Wash liquid volume                                                                             500 mls                                                      Dosage           1 g/l                                                        Salt concentration                                                                             0.05M                                                        Test cloth       Knitted polyester                                            Soil level       ca. 1.9%                                                     ______________________________________                                    

The detergency performance of DHAG, in triolein removal experiments at40° C, with varying ratios of triethylene glycol mono-dodecyl ether (C₁₂EO₃) is shown in FIGS. 1 and 2 for experiments performed in carbonateand borate buffered solutions respectively, DHAG on its own givestriolein removal of about 58% which is comparable to that obtained withC₁₂ EO₈ or C₁₂ EO₆ alone. Mixtures of DHAG and C₁₂ EO₃ give a smallsynergistic improvement.

DHAG by itself exhibits good oil soil detergency (about 58% trioleinremoval at 40° C.). This is comparable to that found for C₁₂ EO₆ or C₁₂EO₈. When DHAG is mixed with a low HLB surfactant, triethylene glycolmon-dodecyl ether (C₁₂ EO₃), a small degree of synergy is observed.Similar detergency results are obtained whether borate orcarbonate-buffered solutions are used.

DHAG appears to be a very promising candidate for the replacement ofhigh HLB ethoxylated surfactants as far as oily soil detergency isconcerned.

We claim:
 1. A liquid detergent comprising (percentages by weight):(a) 5-70% of a detergent active mixture wherein said mixture comprises 65 to 100% of a glyceroglycolipid compound having the structure ##STR6## wherein ¹ comprises one to four saccharide units, R or R₁ are the same or different and are hydrogen or a branched or unbranched, saturated or unsaturated, hydrocarbon radical having from about 1 to about 24 carbons; and B is OH or NR₂ R₃, wherein R₂ and R₃ are the same or different and are hydrogen, a branched or unbranched hydrocarbon, saturated or unsaturated radical having 1 to 24 carbons; wherein the NRR₁ group and B group are positionally interchangeable; and wherein at least one of R, R₁, R₂ or R₃ must be a hydrocarbon radical having 1 to 24 carbons; and wherein said mixture further comprises a nonionic surfactant; (b) 0-50% builder; (c) 0-40% electrolyte; (d) 0.01-5% enzyme; (e) 0.1-15% enzyme stabilizer; (f) 0-20% phase regulant; and (g) remainder water and minors.
 2. A liquid detergent according to claim 1, further comprises an additional surfactant which is selected from the group consisting of cationic surfactants zwitterionic surfactants, amphoteric surfactants and mixtures thereof. 